CN102512987B - Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane - Google Patents
Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane Download PDFInfo
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- CN102512987B CN102512987B CN201110409419.9A CN201110409419A CN102512987B CN 102512987 B CN102512987 B CN 102512987B CN 201110409419 A CN201110409419 A CN 201110409419A CN 102512987 B CN102512987 B CN 102512987B
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Abstract
The invention discloses a method for preparing a high-flux polyvinylidene fluoride hollow fiber membrane. The method comprises the following steps of: mixing polyvinylidene fluoride, a gaseous pore-forming agent, a hydrophilic modifier, additives and organic solvents and making a membrane-making solution; allowing an internal gelling medium and the membrane-making solution to pass through spinning nozzles on dry/wet spinning equipment at the same time, injecting into an external gelling medium, and performing phase-splitting treatment to make a primary membrane; and performing special chemical treatment on the primary membrane with a chemical treatment liquid to obtain a high-flux polyvinylidene fluoride hollow fiber membrane. The invention is characterized in that the membrane is reinforced with the pores by chemical reactions between the internal gelling medium, external gelling medium and chemical treatment liquid and the gaseous pore-forming agent; and the polyvinylidene fluoride hollow fiber membrane has a high flux, a high strength, a high entrapment rate and good hydrophilicity.
Description
Technical field
The present invention relates to a kind of preparation method of Pvdf Microporous Hollow Fiber Membrane, particularly a kind of preparation method of high-throughout Pvdf Microporous Hollow Fiber Membrane.
Background technology
Polyvinylidene fluoride film is a kind of perforated membrane occurring in the last few years, and it has, and good chemical stability is high, good heat resistance and the advantage such as resistance tocrocking is strong, thereby is widely used in the isolated by filtration in each field.But because of the typical linear polymeric structure of Kynoar and extremely strong hydrophobic property, make Pvdf Microporous Hollow Fiber Membrane in actual application, have intensity difference, yielding, the problem such as not withstand voltage, flux is low.In order to improve the application feature of Pvdf Microporous Hollow Fiber Membrane, patent publication No. is by Kynoar in CN1128176A, solvent, macromolecule pore former, non-solvent, the mixing such as surfactant, by the interaction between them, prepare Stability Analysis of Structures, the good hollow-fibre membrane of flux, but film mechanical strength prepared by the method is not enough, flux is not high, can not meet Production requirement.In document [research of nano inorganic/Kynoar composite hyperfiltration membrane], propose pvdf membrane material and various inorganic nanoparticles blend, utilize inorganic nanoparticles to carry out composite modified to pvdf membrane material, by the netted lattice of interaction formation inorganic-organic between the two, prepare the milipore filter with higher voltage endurance capability, but add merely the milipore filter porosity compact structure of inorganic nanoparticles, aperture and hole density are not high, cannot meet high-throughout film industrial requirement.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, propose a kind of preparation method of high-throughout Pvdf Microporous Hollow Fiber Membrane.The method is different from the existing Pvdf Microporous Hollow Fiber Membrane that only utilizes hydrophilic modifier, single one or more method inorganic and organic pore former stripping pore of interpolation to obtain large flux, the method that the present invention proposes by adding gas pore-foaming agent in casting solution, and with special inner gel medium, outer gel media and chemical pretreatment solution, film silk is carried out to special chemical phase-splitting and process, the pore process of strengthening hollow-fibre membrane, obtains a kind of high porosity, high flux, high strength, hollow-fibre membrane that performance is more stable thereby prepare.
The object of the invention is to realize by following technical proposals.
A preparation method for high-throughout Pvdf Microporous Hollow Fiber Membrane, is characterized in that, comprises the following steps:
1) preparation of preparation liquid: by Kynoar, gas pore-foaming agent, hydrophilic modifier, additive, organic solvent at 40-80 ℃ of temperature, be uniformly mixed according to a certain percentage, standing and defoaming, obtain the preparation liquid of constant temperature;
2) preparation of hollow-fibre membrane: utilize dry-jet wet-spinning silk equipment under the spinning speed of setting, inner gel medium and preparation liquid are passed through to the spinning nozzle on dry-jet wet-spinning silk equipment simultaneously, inject outer gel media phase-splitting and obtain just becoming hollow-fibre membrane; To just become hollow-fibre membrane to impregnated in chemical pretreatment solution and carry out special chemical processing, and then put into rinsing in the running water under room temperature, solidify, obtain high-throughout Pvdf Microporous Hollow Fiber Membrane.
Of the present invention being further characterized in that:
Described preparation liquid is prepared from according to the raw material of following mass percent:
Kynoar 10-20%, gas pore-foaming agent 2-8%, hydrophilic modifier 3-8%, additive 0-10%, organic solvent 65-85%.
Described gas pore-foaming agent is one or more the mixture in calcium carbonate, magnesium carbonate, aluminium powder or magnesium powder.
Described hydrophilic modifier is a kind of in PVP or polymethyl methacrylate.
Described additive is polyethylene glycol, glycerine, SiO
2, Al
2o
3, lithium chloride or thin tripoli one or more mixture.
Described organic solvent is a kind of in dimethylacetylamide, dimethyl formamide or 1-METHYLPYRROLIDONE.
Described inner gel medium is that a kind of in water or water and acetic acid, hydrochloric acid, glycerine is 4-9 according to mass ratio: the mixed liquor that 1 ratio forms; The temperature of inner gel medium is 20-60 ℃.
Described outer gel media is the solution of the 0.1-1mol/L of a kind of and water composition in hydrochloric acid or acetic acid, and the temperature of outer gel media is 20-60 ℃.
It is just to become hollow-fibre membrane to impregnated in chemical pretreatment solution that described special chemical is processed, and chemical pretreatment solution is the hydrochloric acid solution of the 0.5-5mol/L under room temperature, and dip time is 6-12 hour.
Beneficial effect of the present invention and advantage:
(1) hydrophilic modifier adding in casting solution can improve the hydrophily of hollow-fibre membrane, the various additives that add also can affect doughnut film strength and surface texture to some extent, and hydrophilic modifier and various additive can affect the porosity of membrane pore structure and film in various degree simultaneously.
(2) the portion gas pore-foaming agent in film and inner gel medium and outer gel media generation chemical reaction, dissolved by chemical etching and produce loose structure, is conducive to the exchange of non-solvent and solvent and improves minute phase velocity of film; Simultaneously gas pore-foaming agent produces a certain amount of gas with the chemical reaction between inner gel medium and outer gel media, will wash gel layer open and on film surface or inner formation microcellular structure, this pore structure can improve membrane flux to the utmost.
(3), with chemical treatment liquid treatment membrane silk, dense layer surface that can etch film surface and produce uniform pore size distribution, is conducive to increase membrane flux and the overall structure of not destroying film, thereby can guarantees when improving membrane flux, keeps the enough intensity of film filopodium.
(4) by regulating particle size and the consumption of gas pore-foaming agent in film, change the composition of inner gel medium and outer gel media, control concentration and the processing time of acid solution in chemical pretreatment solution, porosity and pore size in adjustable film silk, change membrane flux and rejection.
The specific embodiment
Below by embodiment, the present invention is explained, but is not limitation of the present invention.
Embodiment 1
Preparation process is as follows:
1) preparation of preparation liquid: the Kynoar that is 10-20% by mass percent, 2-8% gas pore-foaming agent, 3-8% hydrophilic modifier, 0-10% additive, 65-85% organic solvent are uniformly mixed at 40-80 ℃ of temperature, standing and defoaming, obtains temperature and is the preparation liquid of 40-80 ℃;
2) preparation of hollow-fibre membrane: utilize dry-jet wet-spinning silk equipment under the spinning speed (5-10m/min) of setting, by inner gel medium (a kind of in water or water and acetic acid, hydrochloric acid, glycerine is 4-9 according to mass ratio: the mixed liquor that 1 ratio forms) with preparation liquid simultaneously by the spinning nozzle on dry-jet wet-spinning silk equipment, injects outer gel media (solution of the 0.1-1mol/L of a kind of and water composition of hydrochloric acid or acetic acid) phase-splitting and obtains the first hollow-fibre membrane that becomes; By just becoming hollow-fibre membrane to be placed in chemical pretreatment solution (hydrochloric acid solution of the 0.5-5mol/L under room temperature), carry out special chemical processing, then put into rinsing in the running water under room temperature, solidify, can be made into high-throughout Pvdf Microporous Hollow Fiber Membrane.
The concrete preparation condition of embodiment 1 is as following table:
The external diameter 1.51mm left and right of gained hollow fiber ultrafiltration membrane, wall thickness is 0.248mm left and right, the pure water flux under 0.1MPa reaches 604L/ (m
2h), the rejection of BSA is remained on more than 90% substantially, hot strength is in 3.25MPa left and right.
Embodiment 2
Preparation process is with embodiment 1, and preparation condition is as following table:
The external diameter 1.48mm left and right of gained hollow fiber ultrafiltration membrane, wall thickness is 0.24mm left and right, the pure water flux under 0.1MPa reaches 463L/ (m
2h), the rejection of BSA is remained on more than 95% substantially, hot strength is in 3.70MPa left and right.
Embodiment 3
Preparation process is with embodiment 1, and preparation condition is as following table:
The external diameter 1.61mm left and right of gained hollow fiber ultrafiltration membrane, wall thickness is 0.30mm left and right,, the pure water flux under 0.1MPa reaches 580L/ (m
2h), the rejection of BSA is remained on more than 90% substantially, hot strength is in 3.21MPa left and right.
Embodiment 4
Preparation process is with embodiment 1, and preparation condition is as following table:
The external diameter 1.51mm left and right of gained hollow fiber ultrafiltration membrane, wall thickness is 0.248mm left and right,, the pure water flux under 0.1MPa reaches 760L/ (m
2h), the rejection of BSA is remained on more than 85% substantially, hot strength is in 2.86MPa left and right.
Embodiment 5
Preparation process is with embodiment 1, and preparation condition is as following table:
The external diameter 1.52mm left and right of gained hollow fiber ultrafiltration membrane, wall thickness is 0.256mm left and right,, the pure water flux under 0.1MPa reaches 520L/ (m
2h), the rejection of BSA is remained on more than 95% substantially, hot strength is in 3.62MPa left and right.
Claims (1)
1. a preparation method for high-throughout Pvdf Microporous Hollow Fiber Membrane, is characterized in that, comprises the following steps:
1) preparation of preparation liquid: by Kynoar, gas pore-foaming agent, hydrophilic modifier, additive, organic solvent at 40-80 ℃ of temperature, be uniformly mixed according to a certain percentage, standing and defoaming, obtain the preparation liquid of constant temperature;
2) preparation of hollow-fibre membrane: utilize dry-jet wet-spinning silk equipment under the spinning speed of setting, inner gel medium and preparation liquid are passed through to the spinning nozzle on dry-jet wet-spinning silk equipment, and the outer gel media phase-splitting of injection obtains just becoming hollow-fibre membrane simultaneously; To just become hollow-fibre membrane to impregnated in chemical pretreatment solution and carry out special chemical processing, and then put into rinsing in the running water under room temperature, solidify, obtain high-throughout Pvdf Microporous Hollow Fiber Membrane;
Described preparation liquid is prepared from according to the raw material of following mass percent:
Kynoar 10-20%, gas pore-foaming agent 2-8%, hydrophilic modifier 3-8%, additive 0-10%, organic solvent 65-85%;
Described gas pore-foaming agent is one or more the mixture in calcium carbonate, magnesium carbonate, aluminium powder or magnesium powder;
Described hydrophilic modifier is a kind of in PVP or polymethyl methacrylate;
Described additive is polyethylene glycol, glycerine, SiO
2, Al
2o
3, lithium chloride or thin tripoli one or more mixture;
Described organic solvent be dimethylacetylamide, dimethyl formamide or N ?a kind of in methyl pyrrolidone;
Described inner gel medium is the mixed liquor that ratio that a kind of in water or water and acetic acid, hydrochloric acid, glycerine is 4-9: 1 according to mass ratio forms, and the temperature of inner gel medium is 20-60 ℃;
Described outer gel media is the solution of 0.1-1mol/L of a kind of and water composition in hydrochloric acid or acetic acid, and the temperature of outer gel media is 20-60 ℃;
It is just to become hollow-fibre membrane to impregnated in chemical pretreatment solution that described special chemical is processed, and chemical pretreatment solution is the hydrochloric acid solution of 0.5-5mol/L under room temperature, and dip time is 6-12 hours.
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| CN201110409419.9A CN102512987B (en) | 2011-12-09 | 2011-12-09 | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane |
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| CN201110409419.9A CN102512987B (en) | 2011-12-09 | 2011-12-09 | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane |
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| CN102512987B true CN102512987B (en) | 2014-03-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102764596B (en) * | 2012-07-17 | 2014-05-14 | 西安建筑科技大学 | Preparation method of hydrophilic ultra-filtration membrane |
| CN102941027B (en) * | 2012-11-30 | 2014-11-19 | 艾特克控股集团有限公司 | Method for producing high-flux ultra-filtration membrane |
| CN103349920B (en) * | 2013-06-06 | 2015-07-01 | 西安建筑科技大学 | Dynamic-crosslinking preparation method of polyvinyl alcohol-blended hollow-fiber ultrafiltration membrane |
| CN104587850A (en) * | 2015-01-11 | 2015-05-06 | 王丽莉 | Preparation method of polyvinylidene fluoride hollow fiber membrane |
Citations (6)
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|---|---|---|---|---|
| CN1128176A (en) * | 1995-11-24 | 1996-08-07 | 天津纺织工学院膜天膜技术工程公司 | Polyvinylidene fluoride hollow fibre porous membrane manufacturing method |
| EP1669128A1 (en) * | 2003-08-06 | 2006-06-14 | Zhejiang Omex Environmental Engineering Ltd. | The preparation method of exo-pressure type poly(vinylidene fluoride) hollow fiber membrane spinned utilizing a immersion-coagulation method and the product thereof |
| CN1966132A (en) * | 2005-11-15 | 2007-05-23 | 深圳市诚德来实业有限公司 | PVC hollow fiber ultrafiltration membrane preparation method |
| CN101108314A (en) * | 2006-07-21 | 2008-01-23 | 谭德粹 | Method of preparing polyethersulfone millipore filter membrane strengthened formed pore and use thereof |
| CN101138706A (en) * | 2006-09-04 | 2008-03-12 | 胡萍 | Bunchiness hollow fiber film and method of preparing the same |
| CN102266728A (en) * | 2011-07-05 | 2011-12-07 | 惠州七芯膜净化环保有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
-
2011
- 2011-12-09 CN CN201110409419.9A patent/CN102512987B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1128176A (en) * | 1995-11-24 | 1996-08-07 | 天津纺织工学院膜天膜技术工程公司 | Polyvinylidene fluoride hollow fibre porous membrane manufacturing method |
| EP1669128A1 (en) * | 2003-08-06 | 2006-06-14 | Zhejiang Omex Environmental Engineering Ltd. | The preparation method of exo-pressure type poly(vinylidene fluoride) hollow fiber membrane spinned utilizing a immersion-coagulation method and the product thereof |
| CN1966132A (en) * | 2005-11-15 | 2007-05-23 | 深圳市诚德来实业有限公司 | PVC hollow fiber ultrafiltration membrane preparation method |
| CN101108314A (en) * | 2006-07-21 | 2008-01-23 | 谭德粹 | Method of preparing polyethersulfone millipore filter membrane strengthened formed pore and use thereof |
| CN101138706A (en) * | 2006-09-04 | 2008-03-12 | 胡萍 | Bunchiness hollow fiber film and method of preparing the same |
| CN102266728A (en) * | 2011-07-05 | 2011-12-07 | 惠州七芯膜净化环保有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
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